A Bispidine Iron(IV)–Oxo Complex in the Entatic State
Corresponding Author
Prof. Dr. Peter Comba
Universität Heidelberg, Anorganisch-Chemisches Institut und Interdisziplinäres Zentrum für Wissenschaftliches Rechnen (IWR), INF 270, 69120 Heidelberg, Germany
Search for more papers by this authorCorresponding Author
Prof. Dr. Shunichi Fukuzumi
Department of Chemistry and Nano Science, Ewha Womans University, Seoul, 120-750 Korea
Faculty of Science and Engineering, Meijo University, Nagoya, Aichi, 468-8502 Japan
Search for more papers by this authorCarsten Koke
Universität Heidelberg, Anorganisch-Chemisches Institut und Interdisziplinäres Zentrum für Wissenschaftliches Rechnen (IWR), INF 270, 69120 Heidelberg, Germany
Search for more papers by this authorDr. Bodo Martin
Universität Heidelberg, Anorganisch-Chemisches Institut und Interdisziplinäres Zentrum für Wissenschaftliches Rechnen (IWR), INF 270, 69120 Heidelberg, Germany
Search for more papers by this authorDr. Anna-Maria Löhr
Universität Heidelberg, Anorganisch-Chemisches Institut und Interdisziplinäres Zentrum für Wissenschaftliches Rechnen (IWR), INF 270, 69120 Heidelberg, Germany
Search for more papers by this authorJohannes Straub
Universität Heidelberg, Anorganisch-Chemisches Institut und Interdisziplinäres Zentrum für Wissenschaftliches Rechnen (IWR), INF 270, 69120 Heidelberg, Germany
Search for more papers by this authorCorresponding Author
Prof. Dr. Peter Comba
Universität Heidelberg, Anorganisch-Chemisches Institut und Interdisziplinäres Zentrum für Wissenschaftliches Rechnen (IWR), INF 270, 69120 Heidelberg, Germany
Search for more papers by this authorCorresponding Author
Prof. Dr. Shunichi Fukuzumi
Department of Chemistry and Nano Science, Ewha Womans University, Seoul, 120-750 Korea
Faculty of Science and Engineering, Meijo University, Nagoya, Aichi, 468-8502 Japan
Search for more papers by this authorCarsten Koke
Universität Heidelberg, Anorganisch-Chemisches Institut und Interdisziplinäres Zentrum für Wissenschaftliches Rechnen (IWR), INF 270, 69120 Heidelberg, Germany
Search for more papers by this authorDr. Bodo Martin
Universität Heidelberg, Anorganisch-Chemisches Institut und Interdisziplinäres Zentrum für Wissenschaftliches Rechnen (IWR), INF 270, 69120 Heidelberg, Germany
Search for more papers by this authorDr. Anna-Maria Löhr
Universität Heidelberg, Anorganisch-Chemisches Institut und Interdisziplinäres Zentrum für Wissenschaftliches Rechnen (IWR), INF 270, 69120 Heidelberg, Germany
Search for more papers by this authorJohannes Straub
Universität Heidelberg, Anorganisch-Chemisches Institut und Interdisziplinäres Zentrum für Wissenschaftliches Rechnen (IWR), INF 270, 69120 Heidelberg, Germany
Search for more papers by this authorAbstract
For a series of FeIV=O complexes with tetra- and pentadentate bispidine ligands, the correlation of their redox potentials with reactivity, involving a variety of substrates for alkane hydroxylation (HAT), alkene epoxidation, and phosphine and thioether oxidation (OAT) are reported. The redox potentials span approximately 350 mV and the reaction rates over 8 orders of magnitude. From the experimental data and in comparison with published studies it emerges that electron transfer and the driving force are of major importance, and this is also supported by the DFT-based computational analysis. The striking difference of reactivity of two isomeric systems with pentadentate bispidines is found to be due to a destabilization of the S=1 ground state of one of the ferryl isomers, and this is supported by the experimentally determined redox potentials and published stability constants with a series of first-row transition metal ions with these two isomeric ligands.
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